CN113044827A - Nano carbon material composite biomass hard carbon electrode material and preparation method and application thereof - Google Patents
Nano carbon material composite biomass hard carbon electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a nano carbon material composite biomass hard carbon electrode material, which takes biomass as a raw material, and the biomass hard carbon electrode material is primarily crushed, cleaned and dried; heating with alkali solution, washing, drying, crushing for the second time, heating with acid solution to remove excessive inorganic salt impurity, washing, and drying; adding uniformly dispersed acid liquor of graphene oxide and carbon nanotubes, stirring and mixing uniformly, treating by a microwave hydrothermal method, drying, and crushing for the third time to obtain a composite biomass hard carbon precursor; carrying out low-temperature pre-carbonization and high-temperature treatment on the composite biomass hard carbon precursor under the protection of inert atmosphere to obtain a composite biomass hard carbon material; the nano carbon material composite biomass hard carbon material adjusts the crosslinking degree of a carbon structure by controlling the pyrolysis speed, so that the distribution, the quantity, the size and the like of holes are adjusted; the graphene and the carbon nano tube are added to improve the specific surface area, the electrical conductivity and the thermal conductivity of the material and enhance the structural stability.
Description
The technical field is as follows:
the invention relates to the field of electrochemical energy storage, in particular to a nano carbon material composite biomass hard carbon electrode material and a preparation method and application thereof.
Background art:
electrochemical energy storage devices are important in the storage and utilization of clean energy, and are widely applied in the fields of automobile industry, aerospace, power grids, military equipment, mobile communication, microelectronics and the like. The carbon material has the characteristics of rich raw materials, low price, simple synthesis, stable chemical performance, low working potential, wide working temperature range and the like, and is suitable for being used as an electrode material of an electrochemical energy storage device.
The biomass has a loose structure and a developed primary pore structure, and the carbon material obtained after carbonization treatment can inherit part of the pore structure. The biomass carbon material has the characteristics of wide source, simple process method, lower cost, environmental protection, large specific surface area, high chemical stability and the like. However, during the process of preparing biomass carbon material by pyrolysis, carbon atoms are easy to agglomerate, and active sites of the material are reduced. At present, the biomass hard carbon has the defects of large irreversible capacity, low first efficiency, low discharge voltage and the like, and the application of the biomass hard carbon in the aspect of energy storage is greatly limited.
The invention content is as follows:
aiming at the defects of the prior art, the invention provides a nano carbon material composite biomass hard carbon electrode material which has the advantages of large specific surface area, high conductivity, high specific capacity, good rate performance and excellent energy storage performance, and can be widely applied to the field of electrochemical energy storage
The invention realizes the technical purpose through the following technical means, and a preparation method of a nano carbon material composite biomass hard carbon electrode material comprises the following steps:
a. cleaning a biomass raw material, drying at 60-120 ℃, and primarily crushing to obtain 16-60-mesh particles A after drying;
b. putting the particles A into an alkaline solution with the concentration of 1-5mol/L, heating and stirring for 1-12h at the temperature of 90-120 ℃, then washing with deionized water, filtering or centrifuging until the mixed solution is neutral, then carrying out solid-liquid separation, drying solid substances at the temperature of 60-120 ℃ after separation, and carrying out secondary crushing to obtain 100-mesh 400-mesh powder B;
c. putting the powder B into an acid solution with the concentration of 1-5mol/L, heating and stirring at 90-120 ℃ for 1-12h, washing with deionized water, performing suction filtration or centrifugation until the mixed solution is neutral, performing solid-liquid separation, and drying solid substances at 60-120 ℃ after separation to obtain powder C;
d. uniformly stirring and mixing the powder C and the dispersion liquid D, placing the mixture in a microwave reaction kettle, carrying out microwave hydrothermal reaction for 0.5-2h at the temperature of 100-220 ℃ in a closed state with the microwave power of 0.4-1kW, drying the mixture at the temperature of 60-120 ℃, and crushing the dried mixture for the third time to obtain a 1000-mesh 2000-mesh composite biomass hard carbon precursor E;
e. under the protection of nitrogen or argon inert atmosphere, carrying out low-temperature pre-carbonization on the composite biomass hard carbon precursor E at the temperature of 300-650 ℃ for 1-6h at the heating speed of 1-20 ℃/min to obtain a composite biomass pre-carbonized material F;
f. then, under the protection of nitrogen or argon inert atmosphere, treating the composite biomass pre-carbonization material F at a heating speed of 1-20 ℃/min at a high temperature of 850-1500 ℃ for 1-6h to obtain a composite biomass hard carbon material G;
g. and adding PVDF (polyvinylidene fluoride) dissolved in N-methyl pyrrolidone into the composite biomass hard carbon material G according to the mass ratio of 95:5, and uniformly mixing to obtain a composite biomass hard carbon electrode material H, wherein the mass fraction of the NMP solution of the PVDF is 0.9-5%.
Preferably, the biomass is one or more of coconut shell, straw, bamboo straw and tobacco straw.
Preferably, the dispersion liquid D in the step D is prepared by mixing graphene oxide, carbon nanotubes and PVP according to a mass ratio of 1-10: 0.1-1, and specifically, a PVP surfactant is used as a dispersing agent to prepare a uniform dispersion liquid D of the graphene oxide and the carbon nanotubes in 0.05-1mol/L diluted acid in a stirring or ultrasonic mode.
Preferably, the alkali solution in step b is potassium hydroxide, sodium hydroxide or ammonia water.
Preferably, the acid solution in step c is hydrochloric acid or nitric acid.
A nano carbon composite biomass hard carbon electrode material is prepared by the method.
The application of the nano carbon material composite biomass hard carbon electrode material comprises the nano carbon material composite biomass hard carbon electrode material serving as a composite biomass hard carbon electrode for electrochemical energy storage.
According to the invention, the biomass material is heated in the alkaline solution, so that chemical bonds among cellulose, hemicellulose and lignin are broken, part of lignin is removed, the formed defects are utilized to strengthen pore etching, and the formation of three-dimensional multilevel pore channels is promoted, so that the carbon material not only has abundant energy storage sites, but also has the rate capability of large-current charge and discharge. The microwave hydrothermal treatment is carried out on the biomass under the acidic condition, so that the graphene, the carbon nano tube and the biomass material are effectively compounded, and the first efficiency of the composite biomass hard carbon material is improved. The nano carbon materials such as graphene and carbon nano tubes are used as dopants, the electrical conductivity and the thermal conductivity of the material can be improved by utilizing the excellent electrical conductivity and the thermal conductivity of the graphene, and the interface property of hard carbon is improved; the carbon nano tube can be used for enhancing the structural stability of the composite material, increasing the pore structure and effectively inhibiting the agglomeration phenomenon and the lamination phenomenon of graphene sheets during biomass carbonization. Through the synergistic effect among the graphene, the carbon nano tube and the hard carbon, the advantages of the graphene, the carbon nano tube and the hard carbon are fully exerted, and the structure and the property are complementary. The composite biomass hard carbon material has the advantages of the traditional hard carbon material and the advantages of the nano-doped material, is increased in specific surface area, improved in electrical conductivity, excellent in electrochemical performance, and enhanced in thermal conductivity and structural stability, and has great potential in the application fields of high capacity, high power and high safety.
Has the advantages that: the preparation method of the nano carbon material composite biomass hard carbon electrode material disclosed by the invention has the following beneficial effects:
the prepared composite biomass hard carbon material has a three-dimensional hierarchical porous structure, is large in specific surface area, good in conductivity, high in electron migration speed, large in ion or electron capacity, high in specific capacity, good in rate capability and excellent in energy storage performance, and can be widely applied to the field of electrochemical energy storage, such as a supercapacitor, a lithium ion battery or a sodium ion battery;
the whole preparation process is simple, easy for industrial production, low in cost, green and environment-friendly, and can realize large-scale industrial synthesis.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
The invention relates to a preparation method of a nano carbon material composite biomass hard carbon electrode material, which comprises the following steps:
a. cleaning biomass raw materials such as coconut shells, straws, bamboo straws, tobacco straws and the like, drying at 60-120 ℃, and primarily crushing after drying to obtain particles A with 16-60 meshes;
b. putting the particles A into potassium hydroxide, sodium hydroxide or ammonia water solution with the concentration of 1-5mol/L, heating and stirring for 1-12h at the temperature of 90-120 ℃, then washing with deionized water, carrying out suction filtration or centrifugation until the mixed solution is neutral, then carrying out solid-liquid separation, drying solid substances at the temperature of 60-120 ℃ after separation, and carrying out secondary crushing to obtain 100-mesh 400-mesh powder B;
c. adding the powder B into a hydrochloric acid or nitric acid solution with the concentration of 1-5mol/L, heating and stirring at 90-120 ℃ for 1-12h, washing with deionized water, performing suction filtration or centrifugation until the mixed solution is neutral, performing solid-liquid separation, and drying solid substances at 60-120 ℃ after separation to obtain powder C;
d. using PVP surfactant as a dispersing agent, and preparing a uniform dispersion liquid D of graphene oxide and carbon nano tubes in 0.05-1mol/L diluted acid in a stirring or ultrasonic mode, wherein the mass ratio of the graphene oxide to the carbon nano tubes to the PVP is 1-10: 0.1-1;
e. uniformly stirring and mixing the powder C and the dispersion liquid D, placing the mixture in a microwave reaction kettle, carrying out microwave hydrothermal reaction for 0.5-2h at the temperature of 100-220 ℃ in a closed state with the microwave power of 0.4-1kW, drying the mixture at the temperature of 60-120 ℃, and crushing the dried mixture for the third time to obtain a 1000-mesh 2000-mesh composite biomass hard carbon precursor E;
f. under the protection of nitrogen or argon inert atmosphere, carrying out low-temperature pre-carbonization on the composite biomass hard carbon precursor E at the temperature of 300-650 ℃ for 1-6h at the heating speed of 1-20 ℃/min to obtain a composite biomass pre-carbonized material F;
g. then, under the protection of nitrogen or argon inert atmosphere, treating the composite biomass pre-carbonization material F at a uniform heating speed of 1-20 ℃/min at the high temperature of 850-1500 ℃ for 1-6h to obtain a composite biomass hard carbon material G;
h. and adding PVDF (polyvinylidene fluoride) dissolved in N-methyl pyrrolidone into the composite biomass hard carbon material G according to the mass ratio of 95:5, and uniformly mixing to obtain a composite biomass hard carbon electrode material H. The mass fraction of the NMP solution of PVDF is 0.9-5%.
The nano carbon material composite biomass hard carbon electrode material prepared according to the steps can be used as an electrode material for chemical energy storage, and specifically comprises the following steps: coating a layer of conductive slurry (with the thickness of 1-3 mu m on one surface) consisting of one or more conductive agents of CNT, GO and SP on the surface of aluminum or copper foil, perforated foil of aluminum or copper, aluminum or copper or nickel foam metal, coating a layer of composite biomass hard carbon electrode material H on the surface of the conductive slurry, tabletting under the pressure of 5-20MPa, compacting to the thickness of 50-70 mu m, and drying in a dryer at 60 ℃ for 8 hours in vacuum to ensure that the solvent is completely removed, thereby obtaining the composite biomass hard carbon electrode with the multi-level pore channel flaky sandwich structure.
The button cell testing method used by the invention comprises the following steps: taking a composite or pure biomass hard carbon electrode as a negative electrode, a lithium sheet as a counter electrode and 1M LiPF6The button cell is assembled by using a mixed solution of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) in a mass ratio of 1:3 as an electrolyte and a PE/PP/PE composite membrane as a diaphragm, and charging and discharging are carried out at the voltage of 0.005-2V at the current density of 0.2C and 5C.
The invention provides a preparation method of a nanocarbon material composite biomass hard carbon electrode material, although Graphene (GO) has a large specific surface area and excellent electronic conductivity and thermal conductivity, the lamination phenomenon of graphene sheet layers can hinder ion transmission, and the energy density and the power density of the material are reduced. Therefore, the graphene is compounded with the biomass hard carbon, so that the agglomeration of the graphene can be effectively reduced, the contact sites of active substances can be increased, and the interface property of the hard carbon is improved. Meanwhile, the Carbon Nano Tube (CNT) is doped in the carbon material, so that the structural stability of the composite material can be enhanced, the agglomeration phenomenon during biomass carbonization and the lamination phenomenon of graphene sheet layers are inhibited, the pore structure is increased, more ion storage places are provided, the diffusion dynamics of ions are accelerated, and the ionic conductivity and the electronic conductivity are improved. Through the synergistic effect among the graphene, the carbon nano tube and the hard carbon, the advantages of the graphene, the carbon nano tube and the hard carbon are fully exerted, and the structure and the property are complementary, so that the electrochemical performance of the composite material is more excellent than that of a single material. The obtained composite hard carbon material has rich energy storage sites of carbon materials, high mass specific capacitance, improved electrical conductivity and thermal conductivity, and improved first efficiency, circulation stability and rate capability.
Example 1
The embodiment provides a nano carbon material composite biomass hard carbon electrode material, which is prepared by the following steps:
a. cleaning coconut shells, drying the coconut shells in vacuum at 60 ℃, and crushing the coconut shells by using a crusher to obtain particles A with 30 meshes;
b. putting the particles A into a potassium hydroxide aqueous solution with the concentration of 1mol/L, heating and stirring for 6 hours at the temperature of 100 ℃, repeatedly washing and centrifuging by using deionized water until the mixed solution is neutral, then carrying out solid-liquid separation, drying solid substances in vacuum at the temperature of 60 ℃, and crushing for the second time by using a crusher to obtain 100-mesh powder B;
c. putting the powder B into a nitric acid solution with the concentration of 1mol/L, heating and stirring for 6 hours at 100 ℃, repeatedly washing with deionized water, centrifuging until the mixed solution is neutral, then carrying out solid-liquid separation, and drying solid substances in vacuum at 60 ℃ to obtain powder C;
d. taking PVP surfactant as a dispersing agent, and ultrasonically preparing a uniform dispersion liquid D of graphene oxide and a carbon nano tube in 1mol/L dilute sulfuric acid for 1h, wherein the mass ratio of the graphene oxide to the carbon nano tube to the PVP is 10:10: 1;
e. uniformly stirring and mixing 20g of the powder C and 70mL of the dispersion liquid D, placing the mixture in a microwave reaction kettle with the microwave power of 0.8kW, carrying out microwave hydrothermal reaction for 1h at 120 ℃ in a closed state, then carrying out vacuum drying at 60 ℃ and carrying out third crushing by a crusher to obtain a 1500-mesh composite biomass hard carbon precursor E;
f. under the protection of nitrogen atmosphere, carrying out low-temperature pre-carbonization on the composite biomass hard carbon precursor E at 600 ℃ in a muffle furnace at a heating speed of 10 ℃/min for 2h to obtain a composite biomass pre-carbonized material F;
g. treating the composite biomass pre-carbonized material F in a muffle furnace at the high temperature of 1000 ℃ for 2h at the heating speed of 10 ℃/min under the protection of nitrogen atmosphere to obtain a composite biomass hard carbon material G;
h. and adding PVDF (polyvinylidene fluoride) dissolved in N-methyl pyrrolidone into the composite biomass hard carbon material G according to the mass ratio of 95:5, and uniformly mixing to obtain a composite biomass hard carbon electrode material H. The mass fraction of the NMP solution of PVDF was 5%.
Example 2
The embodiment provides a nano carbon material composite biomass hard carbon electrode material, which is prepared by the following steps:
a. cleaning straws, drying by blasting at 100 ℃, and then primarily crushing by using a crusher to obtain 50-mesh particles A;
b. putting the particles A into a sodium hydroxide aqueous solution with the concentration of 2mol/L, heating and mechanically stirring for 2 hours at 90 ℃, repeatedly washing and filtering by using deionized water until the mixed solution is neutral, then carrying out solid-liquid separation, drying solid substances by blowing at 100 ℃, and carrying out secondary crushing by using a crusher to obtain 150-mesh powder B;
c. putting the powder B into a hydrochloric acid solution with the concentration of 2mol/L, heating and mechanically stirring for 2 hours at 90 ℃, repeatedly washing with deionized water, performing suction filtration until the mixed solution is neutral, performing solid-liquid separation, and drying solid substances by blowing at 100 ℃ to obtain powder C;
d. using PVP surfactant as a dispersing agent, and mechanically stirring for 10 hours to prepare a uniform dispersion liquid D of graphene oxide and carbon nano tubes in 1mol/L dilute nitric acid, wherein the mass ratio of the graphene oxide to the carbon nano tubes to the PVP is 5:10: 1;
e. mechanically stirring and uniformly mixing 20g of the powder C and 70mL of the dispersion liquid D, placing the mixture in a microwave reaction kettle, carrying out microwave hydrothermal reaction for 0.5h at 150 ℃ in a closed state with the microwave power of 1kW, then carrying out blast drying at 100 ℃ and carrying out third crushing by a crusher to obtain a 1200-mesh composite biomass hard carbon precursor E;
f. under the protection of nitrogen atmosphere, carrying out low-temperature pre-carbonization on the composite biomass hard carbon precursor E at the heating speed of 5 ℃/min in a muffle furnace at the temperature of 550 ℃ for 1h to obtain a composite biomass pre-carbonized material F;
g. under the protection of nitrogen atmosphere, treating the composite biomass pre-carbonized material F in a muffle furnace at the high temperature of 900 ℃ for 1h at the uniform heating speed of 5 ℃/min to obtain a composite biomass hard carbon material G;
h. and adding PVDF (polyvinylidene fluoride) dissolved in N-methyl pyrrolidone into the composite biomass hard carbon material G according to the mass ratio of 95:5, and uniformly mixing to obtain a composite biomass hard carbon electrode material H. The mass fraction of the NMP solution of PVDF was 2%.
Example 3
The embodiment provides a nano carbon material composite biomass hard carbon electrode material, which is prepared by the following steps:
a. cleaning bamboo stalks, placing the bamboo stalks under vacuum drying at 80 ℃, and then primarily crushing the bamboo stalks by using a crusher to obtain particles A with 60 meshes;
b. putting the particles A into an ammonia water solution with the concentration of 3mol/L, heating and stirring for 6 hours at 90 ℃, repeatedly washing with deionized water, carrying out suction filtration until the mixed solution is neutral, then carrying out solid-liquid separation, drying solid substances in vacuum at 80 ℃, and crushing for the second time by using a crusher to obtain 200-mesh powder B;
c. putting the powder B into a hydrochloric acid solution with the concentration of 3mol/L, heating and stirring for 6 hours at 90 ℃, repeatedly washing and filtering by deionized water until the mixed solution is neutral, then carrying out solid-liquid separation, and drying solid substances in vacuum at 80 ℃ to obtain powder C;
d. taking PVP surfactant as a dispersing agent, and preparing a uniform dispersion liquid D of graphene oxide and carbon nanotubes in 0.5mol/L dilute sulfuric acid by ultrasonic treatment for 2 hours, wherein the mass ratio of the graphene oxide to the carbon nanotubes to the PVP is 5:10: 1;
e. uniformly stirring and mixing 20g of the powder C and 70mL of the dispersion liquid D, placing the mixture in a microwave reaction kettle with the microwave power of 0.6kW, carrying out microwave hydrothermal reaction for 2 hours at 100 ℃ in a closed state, then carrying out vacuum drying at 80 ℃ and carrying out third crushing by a crusher to obtain a 1800-mesh composite biomass hard carbon precursor E;
f. carrying out low-temperature pre-carbonization on the composite biomass hard carbon precursor E in a tubular furnace at 650 ℃ for 2h at a heating speed of 10 ℃/min under the protection of argon atmosphere to obtain a composite biomass pre-carbonized material F;
g. treating the composite biomass pre-carbonized material F in a tubular furnace at a high temperature of 1200 ℃ for 2h at a uniform heating speed of 10 ℃/min under the protection of argon atmosphere to obtain a composite biomass hard carbon material G;
h. and adding PVDF (polyvinylidene fluoride) dissolved in N-methyl pyrrolidone into the composite biomass hard carbon material G according to the mass ratio of 95:5, and uniformly mixing to obtain a composite biomass hard carbon electrode material H. The mass fraction of the NMP solution of PVDF was 1.5%.
Example 4
The embodiment provides a nano carbon material composite biomass hard carbon electrode material, which is prepared by the following steps:
a. cleaning tobacco stalks, placing the tobacco stalks under 100 ℃ for blast drying, and then primarily crushing the tobacco stalks by using a crusher to obtain 20-mesh particles A;
b. putting the particles A into a sodium hydroxide solution with the concentration of 2mol/L, heating and stirring for 3 hours at 100 ℃, repeatedly washing with deionized water, centrifuging until the mixed solution is neutral, then carrying out solid-liquid separation, drying solid substances by blowing at 100 ℃, and carrying out secondary crushing with a crusher to obtain 100-mesh powder B;
c. putting the powder B into a nitric acid solution with the concentration of 2mol/L, heating and stirring for 3 hours at 100 ℃, repeatedly washing with deionized water, centrifuging until the mixed solution is neutral, performing solid-liquid separation, and drying solid substances by blowing at 100 ℃ to obtain powder C;
d. taking PVP surfactant as a dispersing agent, and preparing a uniform dispersion liquid D of graphene oxide and carbon nanotubes in 0.5mol/L dilute nitric acid by ultrasonic treatment for 2 hours, wherein the mass ratio of the graphene oxide to the carbon nanotubes to the PVP is 10:10: 1;
e. uniformly stirring and mixing 20g of the powder C and 70mL of the dispersion liquid D, placing the mixture in a microwave reaction kettle, carrying out microwave hydrothermal reaction for 1h at 150 ℃ in a closed state with the microwave power of 1kW, then carrying out forced air drying at 100 ℃ and carrying out third crushing by a crusher to obtain a 1600-mesh composite biomass hard carbon precursor E;
f. carrying out low-temperature pre-carbonization on the composite biomass hard carbon precursor E in a tubular furnace at 500 ℃ for 3h at a heating speed of 5 ℃/min under the protection of argon atmosphere to obtain a composite biomass pre-carbonized material F;
g. treating the composite biomass pre-carbonized material F in a tubular furnace at 1300 ℃ for 1h at a uniform heating speed of 5 ℃/min under the protection of argon atmosphere to obtain a composite biomass hard carbon material G;
h. and adding PVDF (polyvinylidene fluoride) dissolved in N-methyl pyrrolidone into the composite biomass hard carbon material G according to the mass ratio of 95:5, and uniformly mixing to obtain a composite biomass hard carbon electrode material H. The mass fraction of the NMP solution of PVDF was 0.9%.
Comparative example 1
The comparative example provides a nanocarbon composite biomass hard carbon electrode material, and the preparation method is consistent with example 1 except that 20g of powder C and 70mL of dispersion liquid D are uniformly stirred and mixed in step e and added into a common hydrothermal reaction kettle for reaction.
Comparative example 2
This comparative example provides a pure biomass hard carbon electrode material prepared according to the same procedure and conditions as example 1 except that no steps d and no step e were used.
Comparative example 3
Under the protection of nitrogen atmosphere, the powder C in the embodiment 1 is subjected to low-temperature pre-carbonization for 2h at 600 ℃ in a muffle furnace at a heating speed of 10 ℃/min to obtain a biomass pre-carbonized material I; mixing and grinding the biomass pre-carbonization material I with the graphene oxide and the carbon nano tube or adding water to the biomass pre-carbonization material I, the graphene oxide and the carbon nano tube for mixing and stirring; under the protection of nitrogen atmosphere, processing for 2h at the high temperature of 1000 ℃ in a muffle furnace at the heating speed of 10 ℃/min; the composite biomass hard carbon material G cannot be prepared.
The results of the electrochemical performance test of each example and comparative example are shown in table 1.
TABLE 1 electrochemical Performance test results of examples and comparative examples
From the test results, the battery prepared by using the nano carbon material composite biomass hard carbon material as the lithium ion battery cathode material has higher specific capacity, higher first charge and discharge efficiency and excellent rate capability compared with the composite biomass hard carbon material and the pure biomass hard carbon material obtained after the common hydrothermal reaction treatment.
The present invention is not intended to be limited to the particular embodiments shown, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. A preparation method of a nano carbon composite biomass hard carbon electrode material is characterized by comprising the following steps:
a. cleaning a biomass raw material, drying at 60-120 ℃, and primarily crushing to obtain 16-60-mesh particles A after drying;
b. putting the particles A into an alkaline solution with the concentration of 1-5mol/L, heating and stirring for 1-12h at the temperature of 90-120 ℃, then washing with deionized water, filtering or centrifuging until the mixed solution is neutral, then carrying out solid-liquid separation, drying solid substances at the temperature of 60-120 ℃ after separation, and carrying out secondary crushing to obtain 100-mesh 400-mesh powder B;
c. putting the powder B into an acid solution with the concentration of 1-5mol/L, heating and stirring at 90-120 ℃ for 1-12h, washing with deionized water, performing suction filtration or centrifugation until the mixed solution is neutral, performing solid-liquid separation, and drying solid substances at 60-120 ℃ after separation to obtain powder C;
d. uniformly stirring and mixing the powder C and the dispersion liquid D, placing the mixture in a microwave reaction kettle, carrying out microwave hydrothermal reaction for 0.5-2h at the temperature of 100-220 ℃ in a closed state with the microwave power of 0.4-1kW, drying the mixture at the temperature of 60-120 ℃, and crushing the dried mixture for the third time to obtain a 1000-mesh 2000-mesh composite biomass hard carbon precursor E;
e. under the protection of nitrogen or argon inert atmosphere, carrying out low-temperature pre-carbonization on the composite biomass hard carbon precursor E at the temperature of 300-650 ℃ for 1-6h at the heating speed of 1-20 ℃/min to obtain a composite biomass pre-carbonized material F;
f. then, under the protection of nitrogen or argon inert atmosphere, treating the composite biomass pre-carbonization material F at a heating speed of 1-20 ℃/min at a high temperature of 850-1500 ℃ for 1-6h to obtain a composite biomass hard carbon material G;
g. and adding PVDF (polyvinylidene fluoride) dissolved in N-methyl pyrrolidone into the composite biomass hard carbon material G according to the mass ratio of 95:5, and uniformly mixing to obtain a composite biomass hard carbon electrode material H, wherein the mass fraction of the NMP solution in the PVDF is 0.9-5%.
2. The preparation method of the nanocarbon material composite biomass hard carbon electrode material as claimed in claim 1, wherein: the biomass is one or more of coconut shell, straw, bamboo stalk and tobacco stalk.
3. The preparation method of the nanocarbon material composite biomass hard carbon electrode material as claimed in claim 1, wherein: and D, mixing the graphene oxide, the carbon nano tube and PVP according to a mass ratio of 1-10: 0.1-1, and specifically, preparing a uniform dispersion liquid D of the graphene oxide and the carbon nano tube in 0.05-1mol/L dilute acid in a stirring or ultrasonic mode by taking a PVP surfactant as a dispersing agent.
4. The preparation method of the nanocarbon material composite biomass hard carbon electrode material as claimed in claim 1, wherein: and the alkali solution in the step b is potassium hydroxide, sodium hydroxide or ammonia water.
5. The preparation method of the nanocarbon material composite biomass hard carbon electrode material as claimed in claim 1, wherein: and the acid solution in the step c is hydrochloric acid or nitric acid.
6. A nano carbon material composite biomass hard carbon electrode material is characterized in that: the nanocarbon composite biomass hard carbon electrode material is prepared by the method of any one of claims 1 to 5.
7. The application of the nano carbon material composite biomass hard carbon electrode material is characterized in that: the composite biomass hard carbon electrode material as claimed in any one of claims 1 to 6 is used as a composite biomass hard carbon electrode for electrochemical energy storage.
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| CN114824225A (en) * | 2022-05-12 | 2022-07-29 | 复旦大学 | Composite negative electrode material doped with nano graphite and preparation method thereof |
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| CN115036473A (en) * | 2022-05-19 | 2022-09-09 | 福州大学 | Hard carbon precursor and doped phase-based sodium ion battery negative electrode material and preparation method thereof |
| CN115557487A (en) * | 2022-11-10 | 2023-01-03 | 泰安市法拉第能源科技有限公司 | Hard carbon negative electrode material for sodium ion battery, preparation method of hard carbon negative electrode material and sodium ion battery |
| CN115557486A (en) * | 2022-11-10 | 2023-01-03 | 泰安市法拉第能源科技有限公司 | Hard carbon negative electrode material, preparation method thereof, negative electrode plate and sodium ion battery |
| CN115557486B (en) * | 2022-11-10 | 2024-02-02 | 泰安市法拉第能源科技有限公司 | Hard carbon negative electrode material, preparation method thereof, negative electrode plate and sodium ion battery |
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